Avermectins substituted in the 4&#34;-position having pesticidal properties

ABSTRACT

What is described are a compound of the formula  
                 
 
     in which  
     R 1  is C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl or C 2 -C 12 alkenyl;  
     R 2  is H, unsubstituted or mono- to pentasubstituted C 1 -C 12 alkyl or unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl;  
     R 3  is C 2 -C 12 alkyl, mono- to pentasubstituted C 1 -C 12 alkyl, unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl; or  
     R 2  and R 3  together are an alkylene or alkenylene bridge;  
     with the proviso that R 1  is not sec-butyl or isopropyl if R 2  is H and R 3  is  2 -hydroxyethyl, isopropyl, n-octyl or benzyl;  
     or, if appropriate, an E/Z isomer, an E/Z isomer mixture and/or a tautomer;  
     a process for preparing and using these compounds and their tautomers; pesticides whose active compound is selected from these compounds and their tautomers; and a process for preparing these compounds and compositions, and the use of these compounds and compositions.

[0001] The invention provides (1) a compound of the formula

[0002] in which

[0003] R₁ is C₁-C₁₂alkyl, C₃-C₈cycloalkyl or C₂-C₁₂alkenyl;

[0004] R₂ is H, unsubstituted or mono- to pentasubstituted C₁-C₁₂alkyl or unsubstituted or mono- to pentasubstituted C₂-C₁₂alkenyl;

[0005] R₃ is C₂-C₁₂alkyl, mono- to pentasubstituted C₁-C₁₂alkyl, unsubstituted or mono- to pentasubstituted C₃-C₁₂cycloalkyl, unsubstituted or mono- to pentasubstituted C₂-C₁₂alkenyl, unsubstituted or mono- to pentasubstituted C₂-C₁₂alkynyl; or

[0006] R₂ and R₃ together are a three- to seven-membered alkylene or a four- to seven-membered alkenylene bridge, in which a CH₂ group may be substituted by O, S or NR₄;

[0007] in which the substituents of the alkyl, alkenyl, alkynyl, alkylene, alkenylene and cycloalkyl radicals mentioned are selected from the group consisting of OH, halogen, halo-C₁-C₂alkyl, CN, NO₂, C₂-C₆alkynyl, C₃-C₈-cycloalkyl which is unsubstituted or substituted by one to three methyl groups, norbornylenyl, C₃-C₈-cycloalkenyl which is unsubstituted or substituted by one to three methyl groups, C₃-C₈halocycloalkyl, C₁-C₁₂alkoxy, C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₈cycloalkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₃-C₈cycloalkylthio, C₁-C₁₂-haloalkylthio, C₁-C₁₂alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₁₂haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl, C₁-C₁₂alkylsulfonyl, C₃-C₈cycloalkylsulfonyl, C₁-C₁₂haloalkylsulfonyl, C₃-C₈halocycloalkylsulfonyl, C₂-C₈alkenyl, C₂-C₈alkynyl, NH(C₁-C₆alkyl), N(C₁-C₆alkyl)₂, —C(═O)R₅, —NHC(═O)R₆, —P(═O)(OC₁-C₆alkyl)₂;

[0008] aryl, heterocyclyl, aryloxy, heterocyclyloxy; and also aryl, heterocyclyl, aryloxy and heterocyclyloxy which, depending on the possibilities of substitution on the ring, are mono- to pentasubstituted by substituents selected from the group consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl, dimethylamino-C₁-C₆alkoxy, C₂-C₈alkenyl, C₂-C₈alkynyl, phenoxy, phenyl-C₁-C₆alkyl; phenoxy which is unsubstituted or mono- to trisubstituted independently of one another by halogen, methoxy, trifluoromethyl or trifluoromethoxy; phenyl-C₁-C₆alkoxy which is unsubstituted or mono- to trisubstituted in the aromatic ring independently of one another by halogen, methoxy, trifluoromethyl or trifluoromethoxy; phenyl-C₂-C₆alkenyl, phenyl-C₂-C₆alkynyl, methylenedioxy, —C(═O)R₅, —O—C(═O)R₆, —NH—C(═O)R₆, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl and C₃-C₈halocycloalkylsulfonyl;

[0009] R₄ is C₁-C₈alkyl, C₃-C₈cycloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, benzyl or —C(═O)—R₅;

[0010] R₅ is H, OH, SH, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₁₂alkylthio, C₂-C₈alkenyloxy, C₂-C₈alkynyloxy; phenyl, phenoxy, benzyloxy, NH-phenyl, —N(C₁-C₆alkyl)-phenyl, NH—C₁-C₆alkyl-C(═O)—R₇, —N(C₁-C₆alkyl)-C₁-C₆alkyl-C(═O)—R₇; or phenyl, phenoxy, benzyloxy, NH-phenyl or —N(C₁-C₆alkyl)-phenyl which are mono to trisubstituted in the aromatic ring independently of one another by halogen, C₁-C₆alkoxy, C₁-C₆haloalkyl or C₁-C₆haloalkoxy;

[0011] R₆ is H, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, phenyl, benzyl, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, —NH-phenyl or —N(C₁-C₁₂alkyl)-phenyl; and

[0012] R₇ is H, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₂-C₈alkenyloxy, phenyl, phenoxy, benzyloxy, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, —NH-phenyl or —N(C₁-C₁₂alkyl)phenyl;

[0013] with the proviso that R₁ is not sec-butyl or isopropyl if R₂ is H and R₃ is 2-hydroxyethyl, isopropyl, n-octyl or benzyl;

[0014] or, if appropriate, an E/Z isomer, E/Z isomer mixture and/or tautomer:

[0015] a process for preparing these compounds, their isomers and tautomers and the use of these compounds, their isomers and tautomers; pesticides whose active compound is selected from these compounds and their tautomers: and a method for controlling pests using these compositions.

[0016] The literature, for example U.S. Pat. No. 4,427,663 proposes certain macrolide compounds for controlling pests. However, the biological properties of these known compounds are not entirely satisfactory, and, as a consequence, there is still a need for providing further compounds having pesticidal properties, in particular for the control of insects and representatives of the order Acarina. According to the invention, this object is achieved by providing the present compounds of the formula (I).

[0017] The compounds claimed according to the invention are derivatives of avermectin. Avermectins are known to the person skilled in the art. They are a group of structurally closely related pesticidally active compounds which are obtained by fermenting a strain of the microorganism Streptomyces avermitilis. Derivatives of avermectins can be obtained by conventional chemical syntheses.

[0018] The avermectins which can be obtained from Streptomyces avermitilis are referred to as A1a, A1b, A2a, A2b, B1a, B1b, B2a and B2b. The compounds referred to as “A” and “B” have a methoxy radical and an OH group, respectively, in the 5-position. The “a” series and the “b” series are compounds in which the substituent R₁ (in position 25) is a sec-butyl radical and an isopropyl radical, respectively. The number 1 in the name of the compounds means that atoms 22 and 23 are linked by double bonds; the number 2 means that they are linked by a single bond and that the C atom 23 carries an OH group. The above nomenclature is adhered to in the description of the present invention to denote the specific structure type in the not naturally occurring avermectin derivatives according to the invention which corresponds to the naturally occurring avermectin. What is claimed according to the invention are derivatives of compounds of the B1 series, in particular mixtures of derivatives of avermectin B1a and avermectin B1b.

[0019] Some of the compounds of the formula (I) can be present as tautomers. Accordingly, hereinabove and hereinbelow, the compounds of the formula (I) are, if appropriate, also to be understood as including the corresponding tautomers, even if the latter are not specifically mentioned in each case.

[0020] Unless defined otherwise, the general terms used hereinabove and hereinbelow have the meanings given below.

[0021] Unless defined otherwise, carbon-containing groups and compounds contain in each case 1 up to and including 6, preferably 1 up to and including 4, in particular 1 or 2, carbon atoms.

[0022] Halogen—as a group per se and also as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio—is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine.

[0023] Alkyl—as a group per se and also as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthio—is, in each case taking into account the number of carbon atoms contained in each case in the group or compound in question, either straightchain, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example

[0024] Cycloalkyl—as a group per se and also as a structural element of other groups and compounds, such as, for example, of halocycloalkyl, cycloalkoxy and cycloalkylthio—is, in each case taking into account the number of carbon atoms contained in each case in the group or compound in question, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

[0025] Alkenyl—as a group per se and also as a structural element of other groups and compounds—is, taking into account the number of carbon atoms and conjugated or isolated double bonds contained in the group, either straight-chain, for example vinyl, allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1,3-hexadienyl or 1,3-octadienyl, or branched, for example isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl. Preference is given to alkenyl groups having 3 to 12, in particular 3 to 6, especially 3 or 4, carbon atoms.

[0026] Alkynyl—as a group per se and also as a structural element of other groups and compounds—is, in each case taking into account the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight-chain, for example ethynyl, propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1,5-heptadien-3-ynyl, or branched, for example 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2-ynyl or 2-methylhept-3-ynyl. Preference is given to alkynyl groups having 3 to 12, in particular 3 to 6, especially 3 or 4, carbon atoms.

[0027] Alkylene and alkenylene are straight-chain or branched bridge members; they are in particular —CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—CH₂—, —CH₂(CH₃)CH₂—CH₂—, —CH₂C(CH₃)₂—CH₂—, —CH₂—CH═CH—CH₂— or —CH₂—CH═CH—CH₂—CH₂—.

[0028] Halogen-substituted carbon-containing groups and compounds, such as, for example, halogen-substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy or alkylthio, can be partially halogenated or perhalogenated, where in the case of polyhalogenation the halogen substituents can be identical or different. Examples of haloalkyl—as a group per se and also as a structural element of other groups and compounds, such as haloalkoxy or haloalkylthio—are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF₂ or CF₃; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃,CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl or isopropyl which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃ or CH(CF₃)₂; butyl or one of its isomers, mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF₃)CHFCF₃ or CH₂(CF₂)₂CF₃; pentyl or one of its isomers, mono- to undecasubstituted by fluorine, chlorine and/or bromine, such as CF(CF₃)(CHF)₂CF₃ or CH₂(CF₂)₃CF₃; and hexyl or one of its isomers, mono- to tridecasubstituted by fluorine, chlorine and/or bromine, such as (CH₂)₄CHBrCH₂Br, CF₂(CHF)₄CF₃, CH₂(CF₂)₄CF₃ or C(CF₃)₂(CHF)₂CF₃.

[0029] Aryl is in particular phenyl, naphthyl, anthracenyl or perylenyl, preferably phenyl.

[0030] Heterocyclyl is in particular pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl, tetrahydrofuranyl, pyranyl, tetrahydropyranyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, quinolinyl, quinoxalinyl, benzofuranyl, benzimidazolyl, benzpyrrolyl, benzthiazolyl, indolyl, cumarinyl or indazolyl, which are preferably attached via a C atom; thienyl, thiazolyl, benzofuranyl, benzothiazolyl, furanyl, tetrahydropyranyl or indolyl is preferred; in particular pyridyl or thiazolyl.

[0031] In the context of the present invention, preference is given to

[0032] (2) compounds according to group (1) of the formula (I) in which R₁ is isopropyl or sec-butyl, preferably to those in which a mixture of the isopropyl and the sec-butyl derivative is present;

[0033] (3) compounds according to group (2) of the formula (I), in which R₂ is H;

[0034] (4) compounds according to group (2) of the formula (I) in which R₂ is C₁-C₈alkyl, in particular methyl;

[0035] (5) compounds according to group (2) of the formula (I) in which R₂ is ethyl;

[0036] (6) compounds according to group (2) of the formula (I) in which R₂ is n-propyl;

[0037] (7) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is unsubstituted or substituted, in particular unsubstituted, C₂-C₅ alkyl;

[0038] (8) compounds according to any of groups (1) to (7) of the formula (I) in which R₃is ethyl;

[0039] (9) compounds according to any of groups (1) to (7) of the formula (I) in which R₃ is n-propyl;

[0040] (10) compounds according to any of groups (2) to (7) of the formula (I) in which R₃ is isopropyl;

[0041] (11) compounds according to any of groups (1) to (7) of the formula (I) in which R₃ is n-butyl, sec-butyl, isobutyl or tert-butyl;

[0042] (12) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is unsubstituted or substituted, in particular unsubstituted, C₆-C₁₂alkyl;

[0043] (13) compounds according to any of groups (1) or (2) of the formula (I) in which R₂ and R₃ together are —CH₂—CH₂—CH₂— or —CH₂—CH₂—CH₂—CH₂—;

[0044] (14) compounds according to any of groups (1) or (2) of the formula (I) in which R₂ and R₃ together are —CH₂—CH₂—O—CH₂—CH₂— or —CH₂—CH₂—N(CH₃)—CH₂—CH₂—;

[0045] (15) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is substituted C₁-C₄alkyl and the substituents are selected from the group consisting of OH, halogen, C₃-C₈cycloalkyl, C₃-C₈cycloalkenyl which is unsubstituted or substituted by one to three methyl groups, C₁-C₁₂alkoxy, C₂-C₈alkynyl, —C(═O)R₅, —NHC(═O)R₆, —P(═O)(OC₁-C₆alkyl)₂; phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, perylenyl and heterocyclyl which are unsubstituted or, depending on the possibility of substitution on the ring, mono- to pentasubstituted;

[0046] and in particular to those in which the substituents of R₃ are selected from the group consisting of halogen, C₃-C₈cycloalkyl, C₂-C₈alkynyl, —C(═O)R₅, —NHC(═O)R₆, —P(═O)(OC₁-C₆alkyl)₂; phenyl, naphthyl, anthracenyl, pyridyl, thiazolyl, imidazolyl, furanyl, quinolinyl, pyrazolyl, which are unsubstituted or, depending on the possibility of substitution on the ring, mono- to trisubstituted;

[0047] (16) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is benzyl which carries, on the aromatic moiety, one to three substituents selected from the group consisting of OH, halogen, CN, NO₂, C₁-C₂alkyl, dimethylamino-C₁-C₄alkoxy, C₃-C₆cycloalkyl, C₁-C₂haloalkyl, C₁-C₂alkoxy, C₁-C₂haloalkoxy, phenoxy, phenyl-C₁-C₆alkyl, phenyl-C₁-C₄alkenyl, unsubstituted or chlorine- or methoxy-substituted phenoxy, unsubstituted or chlorine-, methoxy- or trichloromethyl-substituted benzyloxy, methylenedioxy, —C(═O)R₅, —O—C(═O)R₆ and NHC(═O)R₆;

[0048] R₅ is H, OH, NH₂, NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂, —O—C₁-C₂alkyl-C(═O)—R₇, NHC,—C₂alkyl-C(═O)—R₇, C₁-C₆alkyl, C₁-C₂alkoxy, C₁-C₂alkoxy-C₁-C₂alkoxy, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy; phenyl, phenoxy, benzyloxy, NH-phenyl, NH—C₁-C₆alkyl-C(═O)—R₇; or phenyl, phenoxy, benzyloxy, NH-phenyl which are substituted by halogen, nitro, methoxy, trifluoromethyl or trifluoromethoxy;

[0049] R₆ is H, C₁-C₃alkyl, phenyl or benzyl; and

[0050] R₇ is H, OH, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₂-C₈alkenyloxyl, phenyl, phenoxy, benzyloxy or NH-phenyl;

[0051] (17) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is C₁-C₄alkyl-C(═O)R₅, in particular —CH₂—C(═O)R₅; and

[0052] R₅ is H, OH, NH₂, NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂, C₁-C₄alkyl, C₁-C₁₂alkoxy, C₂-C₄alkenyloxy, phenyl, phenoxy, benzyloxy, NH-phenyl, NH-C₁-C₂alkyl-C(═O)—O—C₁-C₂alkyl-phenyl, —P(═O)(OC₁-C₆alkyl)₂; or phenyl, phenoxy, benzyloxy or NH-phenyl which are substituted by chlorine, fluorine, methoxy, trifluoromethyl or trifluoromethoxy;

[0053] very particularly those in which R₅ is C₁-C₁₂alkoxy;

[0054] (18) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is C₂-C₆alkyl-NHC(═O)R₆ and R₆ is H, C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, phenyl or benzyl;

[0055] (19) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is —CH₂-heterocyclyl and heterocyclyl is pyridyl, furanyl, tetrahydrofuranyl, pyranyl, tetrahydropyranyl, pyrazolyl, imidazolyl, thiazolyl, benzothienyl, quinolinyl, quinoxalinyl, benzofuranyl, benzimidazolyl, benzopyrrolyl, benzothiazolyl, indolyl, cumarinyl or indazolyl, where the radicals mentioned are unsubstituted or mono- or disubstituted independently of one another by halogen, trifluoromethyl, trifluoromethoxy or nitro; particularly preferably pyridyl, furanyl, pyrazolyl, imidazolyl, thiazolyl, benzimidazolyl, benzopyrrolyl, benzothilazolyl, or indolyl which are unsubstituted or mono- or disubstituted independently of one another by halogen, trifluoromethyl, trifluoromethoxy or nitro; in particular pyridyl or thiazolyl which are unsubstituted or mono- or disubstituted independently of one another by halogen, trifluoromethyl, trifluoromethoxy or nitro, in particular monosubstituted by chlorine;

[0056] (20) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is C₂-C₁₀alkenyl, in particular C₂-C₄alkenyl, which is unsubstituted or mono- or disubstituted, in particular monosubstituted, by C₂-C₄alkynyl, —C(═O)—C₁-C₄alkoxy, —C(═O)—O—C₁-C₄alkylbenzoyl, phenyl or halogen; in particular those in which R₃ is —CH₂—CH═CH₂;

[0057] (21) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is branched unsubstituted C₄-C₁₀alkyl;

[0058] (22) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is branched substituted C₃-C₁₀alkyl;

[0059] (23) compounds according to any of groups (1) to (6) of the formula (I) in which R₃ is unsubstituted benzyl.

[0060] (24) In the context of the invention, particular preference is given to the compounds of the formula (I) listed in the tables and, if appropriate, to their E/Z isomers and E/Z isomer mixtures; these are in particular the compounds

[0061] 4″-deoxy-4″-epi-N-ethylaminoavermectin B1;

[0062] 4″-deoxy-4″-epi-N-prop-1-ylaminoavermectin B1;

[0063] 4″-deoxy-4″-epi-(N-ethyl-N-methylamino)avermectin B1;

[0064] 4″-deoxy-4″-epi-(N-methyl-N-prop-1-ylamino)avermectin B1;

[0065] 4″-deoxy-4″-epi-(N-isopropyl-N-methylamino)avermectin B1;

[0066] 4″-deoxy-4″-epi-(N-methyl-N-1-propen-3-ylamino)avermectin B1;

[0067] 4″-deoxy-4″-epi-(N-methyl-N-ethoxycarbonylmethylamino)avermectin B1;

[0068] 4″-deoxy-4″-epi-(N-methyl-N-benzylamino)avermectin B1;

[0069] 4″-deoxy-4″-epi-(N-methyl-N-4-difluoromethoxyphenylmethylamino)avermectin B1;

[0070] 4″-deoxy-4″-epi-(N-methyl-N-2,5-dichlorophenylmethylamino)avermectin B1;

[0071] 4″-deoxy-4″-epi-(N-methyl-N-2,5-difluorophenylmethylamino)avermectin B1;

[0072] 4″-deoxy-4″-epi-(N-methyl-N-2,3,4-trifluorophenylmethylamino)avermectin B1;

[0073] 4″-deoxy-4″-epi-(pyrrolidin-1-yl)avermectin B1;

[0074] 4″-deoxy-4″-epi-(azetidin-1-yl)avermectin B1; and

[0075] 4″-deoxy-4″-epi-(N-methyl-N-[3-{2-oxo-2-phenylethoxycarbonyl}allyl]amino)avermectin B1.

[0076] The invention also provides a process for preparing the compounds of the formula (I) and, if appropriate, tautomers thereof, wherein

[0077] (A) to prepare a compound of the formula (I) in which R₁ has the same meanings as given above under (1) for formula (I), R₂ is hydrogen and R₃ is a group R₃₁—CH—R₃₂ in which R₃₁ is C₁-C₆alkyl, phenyl, heterocyclyl or unsubstituted or [sic] substituted C₁-C₆alkyl, phenyl or heterocyclyl and R₃₂ is H or unsubstituted or substituted C₁-C₅alkyl;

[0078] a compound of the formula (I) in which R₁ has the same meanings as given above under (1) for formula (I) and R₂ and R₃ are hydrogen and which is known and can be prepared by known methods is reacted in the presence of a reducing agent with a compound R₃₁—C(═O)—R₃₂ in which R₃₁ and R₃₂ have the same meanings as given above; or

[0079] (B) to prepare a compound of the formula (Ia) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I) and R₃ has the same meanings as given above under (1) for formula (I), except for hydrogen, a compound of the formula (Ia) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I) and R₃ is hydrogen and which can be prepared by methods known per se;

[0080] is reacted with a compound of the formula R₃-Hal in which R₃ has the same meanings as given above under (1) for the formula (I) and Hal is halogen, in particular bromine or iodine; or

[0081] (C) to prepare a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I) and R₃ is hydroxyl-substituted —CH₂—C₁-C₁₁alkyl,

[0082] a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I), R₃ is —C(═O)—R₅-substituted C₁-C₁₁alkyl and R₅ is OH or alkoxy is reacted with a reducing agent; or

[0083] (D) method [sic] to prepare a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I) and R₃ is COOH-substituted C₁-C₁₂alkyl,

[0084] a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I), R₃ is —C(═O)—R₅-substituted C₁-C₁₂alkyl and R₅ is C₁-C₆alkoxy or benzyloxy is reacted with a base or a reducing agent; or

[0085] (E) method [sic] to prepare a compound of the compound (I) in which R₁ and R₃ have the same meanings as given above under (1) for formula (I) and R₂ is methyl,

[0086] a compound of the formula (I) in which R₁ and R₃ have the same meanings as given above under (1) for formula (I) and R₂ is hydrogen is reacted with a compound of the formula methyl-Hal in which Hal is a halogen, in particular bromine or iodine; or with formaldehyde in the presence of a reducing agent; or

[0087] (F) method [sic] to prepare a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I) and R₃ is —C(═O)N(R₈)₂-substituted C₁-C₁₂alkyl and in which the two R₈ independently of one another are H or unsubstituted or substituted C₁-C₁₂alkyl,

[0088] a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I), R₃ is —C(═O)R₅-substituted C₁-C₁₂alkyl and R₅ is OH is reacted with compound of the formula NH(R₈)₂ in which R₈ is H or unsubstituted or substituted C₁-C₁₂alkyl in the presence of a dehydrating agent; or

[0089] (G) method [sic] to prepare a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I) and R₃ is hydroxyl-substituted C₄-C₁₂ alkyl

[0090] a compound of the formula (I) in which R₁ and R₂ have the same meanings as given above under (1) for formula (I), R₃ is —C(═O)—R₅-substituted C₁-C₅alkyl and R₅ is C₁-C₁₂alkoxy is reacted with two moles of a C₁-C₃alkylmagnesium halide or C₁-C₃alkyllithium reagent; or

[0091] (H) method [sic] to prepare a compound of the formula (I) in which R₁ have the same meanings as given above under (1) for formula (I) and R₂ and R₃ together are a three- to seven-membered alkylene or a four- to seven-membered alkenylene bridge and in which one CH₂ group may be replaced by O, S or NR₄ and R₄ has the same meanings as given above under (1) for formula (I);

[0092] a compound of the formula (I) in which R₁ has the same meanings as given above under (1) for formula (I) and R₂ and R₃ are hydrogen is reacted with a compound of the formula Hal-(C₃-C₇alkylene)-Hal or Hal-(C₄-C₇alkenylene)-Hal in which Hal is a halogen, in particular bromine or iodine, and in which one CH₂ group may be replaced by O, S or NR₄, and in which R₄ has the same meanings as given above under (1) for formula (I); or

[0093] (I) method [sic] to prepare a compound of the formula (I) in which R₁ has the same meanings as given above under (1) for formula (I) and R₂ and R₃ are identical and have the same meanings as given above under (1) for formula (I),

[0094] a compound of the formula (I) in which R₁ has the same meanings as given above under (1) for formula (I) and R₂ and R₃ are hydrogen is reacted with two moles of a compound of the formula R₃-Hal in which R₃ has the same meanings as given above for the formula (I) and Hal is halogen, in particular bromine or iodine; or

[0095] (J) method [sic] to prepare a compound of the formula (I) in which R₂ and R₃ are identical and are unsubstituted or mono- to pentasubstituted —CH₂—C₁-C₁₁alkyl, unsubstituted or mono- to pentasubstituted —CH₂—C₁-C₁₁alkenyl or unsubstituted or mono- to pentasubstituted —CH₂—C₁-C₁₁alkynyl,

[0096] a compound of the formula (I) in which R₁ has the same meanings as given above under (1) for formula (I) and R₂ and R₃ are hydrogen is reacted with two moles of a compound of the formula R₃₁—CHO in which R₃₁ is unsubstituted or mono- to pentasubstituted C₁-C₁₁alkyl, unsubstituted or mono- to pentasubstituted C₁-C₁₁alkenyl or unsubstituted or mono- to pentasubstituted C₁-C₁alkynyl in the presence of a reducing agent.

[0097] What has been stated above for tautomers of compounds of the formula (I) applies correspondingly to the tautomers of the starting materials mentioned above and below.

[0098] The reactions described above and below are carried out in a manner known per se, for example in the absence or, usually, in the presence of a suitable solvent or diluent or a mixture thereof, the reaction being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from about −80° C. to the boiling point of the reaction medium, preferably at from about 0° C. to about +150° C., and, if required, in a closed vessel, under superatmospheric pressure in an atmosphere of inert gas and/or under anhydrous conditions. Particularly advantageous reaction conditions can be found in the examples.

[0099] The reaction time is not critical; preference is given to a reaction time of from about 0.1 to about 24 hours, in particular from about 0.5 to about 10 hours.

[0100] The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography, or by any suitable combination of these methods.

[0101] The starting materials mentioned above and below used for preparing compounds of the formula (I) and, if appropriate, and [sic] their tautomers are known or can be prepared by methods known per se, for example in accordance with the specifications below.

[0102] Process Variant (A):

[0103] Examples of solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; carboxylic acids such as acetic acid, formic acid or pivalic acid; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide; and also water; or mixtures of the solvents mentioned;

[0104] particularly suitable are ethers, alcohols, water and carboxylic acids, in particular tetrahydrofuran, acetic acid or water.

[0105] The reactions are advantageously carried out in a temperature range of from about room temperature to the boiling point of the solvent used; preference is given to carrying out the reaction at room temperature.

[0106] In a preferred embodiment of variant (A), the reaction is carried out at room temperature in tetrahydrofuran in the presence of acetic acid. Particularly preferred conditions for the reaction are described in Example H1.1.

[0107] Process Variant (B):

[0108] Examples of solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons and ethers as listed above under process variant (A); ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; carboxylic esters such as methyl acetate, ethyl acetate or esters of benzoic acid; amides as listed above under process variant (A); nitrites, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide; and also water; or mixtures of the solvents mentioned.

[0109] particularly [sic] suitable are water, esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of such an organic solvent with water.

[0110] The reactions are advantageously carried out in a temperature range of from about room temperature to the boiling point of the solvent used, preferably from room temperature to 90° C., in particular to 60° C., and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.

[0111] Particularly preferred conditions for the reaction are described, for example, in Examples H1.2, H1.3, H2.1 and H2.7.

[0112] Process Variant (C):

[0113] Examples of solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons and ethers, amides and nitrites as listed above under process variant (A); and sulfoxides, such as dimethyl sulfoxide; or mixtures of the solvents mentioned; particularly suitable are ethers and hydrocarbons; [sic]

[0114] The reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 0° C. to room temperature. Particularly preferred conditions for the reaction are described, for example, in Example H2.2.

[0115] Process Variant (D):

[0116] Suitable solvents are the same as mentioned under variant (A), and additionally also ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; and carboxylic acids such as acetic acid or formic acid; carboxylic esters such as methyl acetate, ethyl acetate or esters of benzoic acid.

[0117] The reactions are advantageously carried out in a temperature range of from about room temperature to the boiling point of the solvent used, preferably in the presence of an inorganic base such as, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.

[0118] Particularly preferred conditions for this process variant are described, for example, in Example H2.6.

[0119] Alternatively, it is possible to choose a reaction variant in which a reducing agent, in particular molecular hydrogen, in particular in a mixture of tetrahydrofuran and water as solvent and in the presence of a heavy metal catalyst, in particular a Pd catalyst, is used.

[0120] Particularly preferred conditions for this process variant are described, for example, in Example H2.5.

[0121] Process Variant (E):

[0122] Suitable solvents are the same as mentioned under variant (B); particularly suitable are esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of an ester with water.

[0123] The reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from room temperature to 60° C., and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.

[0124] Particularly preferred conditions for this process variant are described, for example, in Example H2.3.

[0125] Suitable for use in an alternative embodiment are the same solvents as mentioned above, preferably ethers, alcohols, water and carboxylic acids, in combination with a hydride such as a borohydride, in particular NaCNBH₃.

[0126] Particularly preferred conditions for this process variant are described, for example, in Example H2.4.

[0127] Process Variant (F):

[0128] Examples of solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons; ethers, amides and nitrites, as listed above under process variant (A); ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; carboxylic esters such as methyl acetate, ethyl acetate or esters of benzoic acid; and sulfoxides, such as dimethyl sulfoxide; or mixtures of the solvents mentioned.

[0129] particularly [sic] suitable are esters of organic acids such as ethyl acetate.

[0130] Suitable for use as dehydrating agent are the customary peptide coupling reagents, in particular carbodiimides and hydroxybenzotriazoles.

[0131] The reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably at room temperature.

[0132] Particularly preferred conditions for the reaction are described, for example, in Example H2.8.

[0133] Process Variant G:

[0134] Examples of solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and ethers as listed above under process variant (A); and sulfoxides, such as dimethyl sulfoxide; or mixtures of the solvents mentioned; particularly suitable are ethers, especially tetrahydrofuran.

[0135] The reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 0° C. to room temperature.

[0136] Particularly preferred conditions for the reaction are described, for example, in Example H2.10.

[0137] Process Variant (H):

[0138] Suitable solvents are the same as mentioned under variant (B), particularly suitable are water, esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of such an organic solvent with water.

[0139] The reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 90° C. to the boiling point of the solvent, and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.

[0140] Particularly preferred conditions for the reaction are described, for example, in Example H3.2.

[0141] Process Variant (I):

[0142] Suitable solvents are the same as mentioned under variant (B), particularly suitable are water, esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of such an organic solvent with water.

[0143] The reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 90° C. to the boiling point, and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.

[0144] Particularly preferred conditions for the reaction are described, for example, in Example H3.1.

[0145] Process Variant (J):

[0146] Suitable solvents are the same as mentioned under variant (B), particularly suitable are water, ethers [sic] of organic acids, alcohols and water; in particular two-phase mixtures of an ether with water.

[0147] The reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably at room temperature.

[0148] Particularly preferred conditions for the reaction are described, for example, in Example H.3.3.

[0149] The compounds of the formula (I) may be present in the form of one of the possible isomers or as a mixture thereof, as pure isomers or as isomer mixtures, i.e. as a racemic mixture; the invention relates both to the pure isomers and the racemic mixtures and should be understood accordingly in each case above and below, even if stereochemical details are not mentioned specifically in each case.

[0150] The racemates may be resolved by known methods into the enantiomers, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one isomer is complexed.

[0151] Apart from resolving corresponding isomer mixtures, optically pure isomers may also be obtained in accordance with the invention by commonly known methods of enantioselective synthesis, for example by performing the process of the invention with starting materials of appropriate stereochemistry.

[0152] Where the individual components possess different biological activity, it is advantageous to isolate or synthesize the respective isomer with higher biological activity.

[0153] The compounds of the formula (I) may also be obtained in the form of their hydrates and/or may include other solvents, examples being those used, where appropriate, for the crystallization of compounds present in solid form.

[0154] The invention relates to all those embodiments of the process which start from a compound obtainable at any stage of the process as a starting material or intermediate and in which all or some of the absent steps are carried out or a starting material is used in the form of a derivative and/or salt and/or its racemates and/or enantiomers or in particular is formed under the reaction conditions.

[0155] In the process of the present invention, it is preferred to use those starting materials and intermediates which lead to the particularly preferred compounds of the formula (I).

[0156] The invention relates in particular to the preparation processes described in the examples.

[0157] The compounds of the invention of the formula (I) are preventively and/or curatively valuable active compounds having a very favourable biocidal and very broad spectrum in the field of pest control, even at low use concentrations, while being favourably tolerated by homeotherms, fish and plants. Surprisingly, they are equally suitable for controlling plant pests and ecto- and endoparasites on humans and especially on useful and domestic animals and pets. They are active against all or individual development stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina, nematodes, cestodes and trematodes, while at the same time sparing useful animals. The insecticidal or acaricidal action of the active compounds of the invention may be manifested directly, i.e. in the death of the pests, which occurs directly or only after a certain time, for example during ecdysis, or indirectly, for example in reduced oviposition and/or hatching rate, the good action corresponding to a kill rate (mortality) of at least 50% to 60%.

[0158] The activity of the compounds according to the invention and of the compositions comprising them against animal pests can be widened considerably and adapted to given circumstances by adding other insecticides, acaricides or nematicides. Suitable additives are, for example, representatives of the following classes of active compounds: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, neonicotinoids and Bacillus thuringiensis preparations.

[0159] Particularly suitable mixing partners are, for example: azamethiphos; chlorfenvinphos, bupirimate; cypermethrin, cypermethrin high-cis; cyromazin; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; jodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; is a substance obtainable from Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromopropylate; methoprene; disulfuton; quinalphos; taufluvalinat; thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin; diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenazaquin; fenobucarb; fenvalerate; formothion; methiocarb; heptenophos; imidacloprid; isoprocarb; methamidophos; methomyl; mevinphos; parathion; parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; abamectin; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; primicarb; pyriproxyfen; pyrimidifen; nematorin; nitenpyram; NI-25, acetamiprid; avermectin B₁ (abamectin); is a plant extract which acts on insects; a preparation which comprises nematodes which act on insects; a preparation obtainable from Bacillus subtilis; a preparation which comprises fungi which act on insects; a preparation which comprises viruses which act on insects; AC 303 630; acephat; acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap; betacyfluthrin; BPMC; brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben; cadusafos; carbaryl; carbopheno-thion; chloethocarb; chlorethoxyfos; chlormephos; cis-resmethrin; clocythrin; clofentezin; cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoat; dimethylvinphos; dioxathion; edifenphos; emametcin; esfenvalerate; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion; ivermectin; lambda-cyhalothrin; malathion; mecarbam; mesulfenphos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoate; oxamyl; oxydemethon M; oxydeprofos; permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M; pirimiphos A; promecarb; propaphos; prothiofos; prothoate; pyrachlophos; pyrada-phenthion; pyresmethrin; pyrethrum; RH 5992; salithion; sebutos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam; tetrachlor-vinphos; thiacloprid; thiamethoxam; thiafenox; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarthen; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; YI 5301/5302; zetamethrin; DPX-MP062; RH-2485; D 2341 or XMC (3,5-xy-lyl methylcarbamate).

[0160] Examples of the animal pests mentioned include those which are set out in the European Patent Application EP-A-736,252, page 5, line 55, to page 6, line 55. The pests mentioned therein are therefore incorporated by reference in the subject-matter of the present invention.

[0161] The compounds according to the invention can also be used to control pests from the class Nematoda. These include, for example,

[0162] root gall nematodes, cyst-forming nematodes, stem nematodes and leaf nematodes; in particular of Heterodera spp., for example Heterodera schachtii, Heterodera avenae and Heterodera trifolii; Globodera spp., for example Globodera rostochiensis; Meloidogyne spp., for example Meloidogyne incoginita and Meloidogyne javanica; Radopholus spp., for example Radopholus simiis; Pratylenchus, for example Pratylenchus neglectans and Pratylenchus penetrans; Tylenchulus, for example Tylenchulus semipenetrans; Longidorus, Trichodorus, Xiphinema, Ditylenchus, Apheenchoides and Anguina; in particular Meloidogyne, for example Meloidogyne incognita, and Heterodera [sic], for example Heterodera glycines.

[0163] In the present invention, particular emphasis is given to using the compounds of the formula (I) according to the invention for protecting plants against parasitic feeding pests.

[0164] The active compounds according to the invention can be used to control pests of the type mentioned which occur on plants, especially on useful plants and ornamentals, in agriculture, in horticulture and in forestry, or on parts of such plants, such as fruits, flowers, foliage, stems, tubers or roots, such control meaning containment or destruction, with the protection against these pests in some cases also extending to plant parts which are formed at a later point in time.

[0165] Particularly suitable target crops include cereals, such as wheat, barley, rye, oats, rice, maize or sorghum, beet, such as sugar beet or fodder beet; fruit, for example pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; pulses, such as beans, lentils, peas or soya beans; oil crops, such as oil seed rape, mustard, poppies, olives, sunflowers, coconut, castor-oil plant, cacao or peanuts; curcurbits, such as squash, cucumbers or melons; fibre crops, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or capsicum; Lauraceae, such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, grapevines, hops, Musaceae, rubber plants and ornamentals.

[0166] Further fields of use of the active compounds according to the invention are in the protection of stored products and stores and of material and also in the hygiene sector, in particular in the protection of domestic and useful animals against pests of the type mentioned, in particular against the infestation of pets, especially cats and dogs, by fleas, ticks and nematodes.

[0167] The invention therefore also relates to pesticide compositions, such as—to be chosen in accordance with the intended objectives and prevailing circumstances—emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, sprayable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations of polymeric materials, which comprise—at least—one of the active compounds according to the invention.

[0168] In these compositions, the active compound is used in pure form, a solid active compound for example in a specific particle size or, preferably, together with—at least—one of the auxiliaries common in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants). For the control of parasites on humans, domestic and useful animals and pets, of course, only physiologically acceptable additives are used.

[0169] Suitable for use as formulation auxiliaries are, for example, solid carriers, solvents, stabilizers, slow-release auxiliaries, colorants and, where appropriate, surface-active compounds (surfactants). Suitable carriers and auxiliaries here include all of the substances commonly used at [lacuna]. Suitable auxiliaries, such as solvents, solid carriers, surface-active compounds, nonionic surfactants, cationic surfactants, anionic surfactants and further auxiliaries in the compositions used in accordance with the invention are, for example, the same as those described in EP-A-736 252, page 7, line 51, to page 8, line 39.

[0170] The compositions for use in crop protection and on humans and domestic and useful animals generally comprise from 0.1 to 99%, in particular from 0.1 to 95%, of active compound and from 1 to 99.9%, in particular from 5 to 99%, of—at least—one solid or liquid auxiliary, it being possible in general for from 0 to 25%, in particular from 0.1 to 20%, of the compositions to comprise surfactants (% denotes in each case per cent by weight). While concentrated compositions tend to be the preferred commercial product, the end user generally uses dilute compositions with substantially lower concentrations of active compounds.

[0171] Preferred crop protection compositions are made up, in particular, as follows (%=per cent by weight): Emulsifiable concentrates: Active compound: 1 to 90%, preferably 5 to 20% Surfactant: 1 to 30%, preferably 10 to 20% Solvent: 5 to 98%, preferably 70 to 85% Dusts Active compound: 0.1 to 10%, preferably 0.1 to 1% Solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates: Active compound: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: Active compound: 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 99%, preferably 15 to 98% Granules: Active compound: 0.5 to 30%, preferably 3 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0172] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rape seed oil or soya bean oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, and also fertilizers or other active compounds for achieving specific effects, for example acaricides, bactericides, fungicides, nematocides, molluscicides or selective herbicides.

[0173] The crop protection compositions according to the invention are prepared in a known manner, in the absence of auxiliaries for example by grinding, sieving and/or compressing a solid active compound or a mixture of active compounds, for example to a particular particle size, and in the presence of at least one auxiliary for example by intimate mixing and/or grinding of the active compound or a mixture of active compounds with the auxiliary or auxiliaries. These processes for preparing the compositions according to the invention and the use of the compounds of the formula (I) for preparing these compositions also form part of the subject-matter of the invention.

[0174] The application techniques for the crop protection compositions, i.e. the methods of controlling pests of the abovementioned type, such as spraying, fogging, dusting, brushing, dressing, scattering or watering, which are to be chosen in accordance with the desired objectives and prevailing circumstances, and the use of the compositions for controlling pests of the abovementioned type are also provided by the invention. Typical use concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active compound. The application rates per hectare are generally from 1 to 2000 g of active compound per hectare, in particular from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

[0175] A preferred application technique in the field of crop protection is that of application to the foliage of the plants (foliar application), the frequency and the rate of application being guided by the intensity of infestation of the pest in question. However, the active compound may also pass into the plants through the root system (systemic action), by the locus of the plants being drenched with a liquid composition or the active compound in solid form being incorporated into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules may be added to the flooded paddy field.

[0176] The crop protection compositions according to the invention are also suitable for protecting plant propagation material, for example seed material, such as fruits, tubers or kernels, or plant cuttings, against animal pests. The propagation material may be treated with the composition prior to planting; seed, for example, may be dressed before sowing. The active compounds of the invention may also be applied to seed kernels (coating) by either drenching the kernels in a liquid composition or coating them with a solid composition. The composition may also be applied to the site of planting where the propagation material is being planted, for example to the seed furrow at the time of sowing. These treatment methods for plant propagation material, and the plant propagation material thus treated, are further provided by the invention.

PREPARATION EXAMPLES Example H1.1 4″-Deoxy-4″-epi-(N-3-fluorophenylmethylamino)-avermectin B1

[0177] 1.0 g of 4″-deoxy-4″-epi-amino-avermectin B1 is dissolved in 12 ml of tetrahydrofuran. 1.8 ml of acetic acid, 0.2 ml of water and 0.18 ml of 3-fluorobenzaldehyde are added. 90 mg of sodium cyanoborohydride are then added. The mixture is stirred at room temperature for 12 hours. The mixture is then extracted with ethyl acetate and saturated sodium chloride solution, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-(N-3-fluorophenylmethylamino)-avermectin B1.

Example H1.2 4″-deoxy-4″-epi-N-ethylamino-avermectin B1

[0178] 4.0 g of 4″-deoxy-4″-epi-amino-avermectin B1 are dissolved in 24 ml of ethyl acetate. 7.4 ml of ethyl iodide and 24 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at room temperature for 14 hours. The phases are then separated, the organic phase is dried over sodium sulfate and the solvents are distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-N-ethylamino-avermectin B1.

Example H1.3 4″-deoxy-4″-epi-N-(isopropoxycarbonylmethyl)amino-avermectin B1

[0179] 300 mg of 4″-deoxy-4″-epi-amino-avermectin B1 are dissolved in 3 ml of ethyl acetate. 620 mg of isopropyl bromoacetate and 3 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at room temperature for 18 hours. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-N-(isopropoxycarbonylmethyl)amino-avermectin B1.

Example H2.1 4″-deoxy-4″-epi-(N-methyl-N-1-propen-3-ylamino)-avermectin B1

[0180] 600 mg of 4″-deoxy-4″-epi-methylamino-avermectin B1 are dissolved in 6 ml of ethyl acetate. 0.56 ml of allyl bromide and 6 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at 60° C. for 18 hours and then cooled. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi(N-methyl-N-1-propen-3-ylamino)-avermectin B1.

Example H2.2 4″-deoxy-4″-epi-(N-2-hydroxyethyl-N-methylamino)-avermectin B1

[0181] Step 1:

[0182] 4.55 g of 4″-deoxy-4″-epi-methylamino-avermectin B1 are dissolved in 45 ml of ethyl acetate. 8.6 g of ethyl bromoacetate and 45 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at 60° C. for 18 hours and then cooled. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-(N-methyl-N-ethoxycarbonylmethylamino)-avermectin B1.

[0183] Step 2:

[0184] 300 mg of 4″-deoxy-4″-epi-(N-methyl-N-ethoxycarbonylmethylamino)-avermectin B1 are dissolved in 6 ml of toluene. With stirring at room temperature, 1.3 ml of diisobutylaluminium hydride (1.2 mol/l in toluene) are added. After 15 minutes, the mixture is extracted with ethyl acetate and saturated ammonium chloride solution. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (ethyl acetate/methanol). This gives 4″-deoxy-4″-epi-(N-2-hydroxyethyl-N-methylamino)-avermectin B1.

Example H2.3 4″-deoxy-4″-epi-(N-isopropyl-N-methylamino)-avermectin B1

[0185] 2.0 g of 4″-deoxy-4″-epi-isopropylamino-avermectin B1 are dissolved in 20 ml of ethyl acetate. 4 ml of methyl iodide and 20 ml of sodium bicarbonate (1N in water) are added and the mixture is stirred vigorously at 60° C. for 14 hours and then cooled. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (ethyl acetate). This gives 4″-deoxy-4″-epi(N-isopropyl-N-methylamino)-avermectin B1.

Example H2.4 4″-deoxy-4″-epi-(N-isopropyl-N-methylamino)-avermectin B1

[0186] 9.14 g of 4″-deoxy-4″-epi-isopropylamino-avermectin B1 are dissolved in 100 ml of methanol. 15 ml of pivalic acid and 25 ml of formaldehyde solution (37% in water) are added. 0.7 g of sodium cyanoborohydride is then added. The mixture is stirred at room temperature for 1 hour, and the methanol is then evaporated under reduced pressure and the residue is extracted with ethyl acetate and saturated sodium bicarbonate solution. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (ethyl acetate/methanol). This gives 4″deoxy-4″-epi-(N-isopropyl-N-methylamino)-avermectin B1.

Example H2.5 4″-deoxy-4″-epi-(N-carboxymethyl-N-methylamino)-avermectin B1

[0187] Step 1:

[0188] 10 g of 4″-deoxy-4″-epi-methylamino-avermectin B1 are dissolved in 100 ml of ethyl acetate. 15.6 g of benzyl bromoacetate and 100 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at 60° C. for 5 days and then cooled. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-(N-benzyloxycarbonylmethyl-N-methylamino)-avermectin B1.

[0189] Step 2:

[0190] 7.8 g of 4″-deoxy-4″-epi-(N-benzyloxycarbonylmethyl-N-methylamino)-avermectin B1 are dissolved in 100 ml of tetrahydrofuran. 780 mg of palladium (5% on carbon) are added, and the hydrogenation is carried out at atmospheric pressure and room temperature. After one hour, the hydrogen uptake has ended. The mixture is filtered through Celite and the solvent is evaporated. This gives 4″-deoxy-4″-epi-(N-carboxymethyl-N-methylamino)-avermectin B1.

Example H2.6 4″-deoxy-4″-epi-(N-carboxymethyl-N-methylamino)-avermectin B1

[0191] Step 1:

[0192] 15 g of 4″-deoxy-4″-epi-methylamino-avermectin B1 are dissolved in 120 ml of ethyl acetate. 26 g of methyl bromoacetate and 120 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at 60° C. for 5 days and then cooled. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-(N-methoxycarbonylmethylamino-N-methyl)-avermectin B1.

[0193] Step 2:

[0194] 10 g of 4″-deoxy-4″-epi-(N-methoxycarbonylmethylamino-N-methyl)-avermectin B1 is [sic] dissolved in 90 ml of tetrahydrofuran. 10 ml of water and 440 mg of lithium hydroxide monohydrate are added, and the mixture is stirred at room temperature for 14 hours. The mixture is then extracted with water and diethyl ether and the aqueous phase is separated off and lyophilized. The residue is extracted with ethyl acetate and citric acid (10% in water), the organic phase is dried over sodium sulfate and the solvent is distilled off. This gives 4″-deoxy-4″-epi-(N-carboxymethyl-N-methylamino)-avermectin B1 [sic].

Example H2.7 4″-deoxy-4″-epi-(N-ethyl-N-methylamino)-avermectin B1

[0195] 8.0 g of 4″-deoxy-4″-epi-N-methylamino-avermectin B1 are dissolved in 50 ml of ethyl acetate. 15 ml of ethyl iodide and 50 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at 60° C. for 2 days. The phases are then separated, the organic phase is dried over sodium sulfate and the solvents are distilled off. The residue is purified by silica gel chromatography (ethyl acetate/methanol). This gives 4″-deoxy-4″-epi-(N-ethyl-N-methylamino)-avermectin B1.

Example H2.8 4″-deoxy-4″-epi-{N-[(1-benzyloxycarbonylethylcarbonyl}methyl]-N-methylamino)-avermectin B1

[0196] 500 mg of 4″-deoxy-4″-epi-(N-carboxymethyl-N-methylamino)-avermectin B are dissolved in 5 ml of ethyl acetate, and 170 ml of benzyl L-alaninate, 72 mg of 1-hydroxy-7-azabenzotriazole and 110 mg of N,N-dicyclohexylcarbodiimide are then added. The mixture is stirred at room temperature for 7 days and then extracted with ethyl acetate and sodium bicarbonate (1N in water). The organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-{N-[(1-benzyloxycarbonylethylcarbamoyl)methyl]-N-methylamino}-avermectin B1.

Example H2.9 4″-deoxy-4″-epi-{N-[(1-carboxyethylcarbamoyl)methyl]-N-methylamino}-avermectin B1

[0197] 160 mg of 4″-deoxy-4″-epi-{N-[(1-benzyloxycarbonylethylcarbamoyl)methyl]-N-methylamino}-avermectin B1 are dissolved in 10 ml of tetrahydrofuran. 50 mg of palladium (5% on carbon) are added and the hydrogenation is carried out at atmospheric pressure and room temperature. After 3 hours, the hydrogen uptake has ended. The mixture is filtered through Celite and the solvent is evaporated. This gives 4″-deoxy-4″-epi-{N-[(1-carboxyethylcarbamoyl)methyl]-N-methylamino}-avermectin B1.

Example H2.10 4″-deoxy-4″-epi-[N-(2-hydroxy-2-methylpropyl]-N-methylamino)-avermectin B1

[0198] 300 mg of 4″-deoxy-4″-epi-(N-methyl-N-ethoxycarbonylmethylamino)-avermectin B1 (step 1 from H2.2) are dissolved in 6 ml of tetrahydrofuran. With stirring, 0.64 ml of methylmagnesium bromide (3 mol/l in diethyl ether) is added at room temperature. After one hour, the mixture is extracted with ethyl acetate and saturated ammonium chloride solution. The phases are then separated, the organic phase is dried over sodium sulfate and the solvents are distilled off. The residue is purified by silica gel chromatography (ethyl acetate/methanol). This gives 4″-deoxy-4″-epi-[N-(2-hydroxy-2-methylpropyl)-N-methylamino]-avermectin B1.

Example H3.1 4″-deoxy-4″-epi-[N,N-bis-(1-phenyl-1-propen-3-yl)amino]-avermectin B1

[0199] 3.48 g of 4″-deoxy-4″-epi-amino-avermectin B1 are dissolved in 40 ml of ethyl acetate. 4.62 g of 3-bromo-1-phenyl-1-propene and 40 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at 60° C. for 3 days and then cooled. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-[N,N-bis-( 1-phenyl-1-propen-3-yl)amino]-avermectin B1.

Example H3.2 4″-deoxy-4″-epi-(azetidin-1-yl)-avermectin B1

[0200] 300 mg of 4″-deoxy-4″-epi-amino-avermectin B1 are dissolved in 1 ml of toluene. 0.106 ml of 1,3-dibromopropane and 1 ml of sodium bicarbonate (1N in water) are added. The mixture is stirred vigorously at 90° C. for 24 hours and then cooled. The phases are then separated, the organic phase is dried over sodium sulfate and the solvent is distilled off. The residue is purified by silica gel chromatography (ethyl acetate/methanol). This gives 4″-deoxy-4″-epi(azetidin-1-yl)-avermectin B1.

Example H3.3 4″-deoxy-4″-epi-[N,N-bis-(3,3- dimethylbutyl)amino]-avermectin B1

[0201] 0.87 g of 4″-deoxy-4″-epi-amino-avermectin B1 is dissolved in 10 ml of tetrahydrofuran. 1 ml of pivalic acid, 0.1 ml of water and 0.60 g of 3,3-dimethylbutyraldehyde are added. 0.38 g of sodium cyanoborohydride are then added. The mixture is stirred at room temperature for 14 hours. The mixture is then extracted with ethyl acetate and sodium bicarbonate (1N in water), the organic phase is dried over sodium sulfate and the solvents are distilled off. The residue is purified by silica gel chromatography (hexane/ethyl acetate). This gives 4″-deoxy-4″-epi-[N,N-bis-(3,3-dimethylbutyl)amino]-avermectin B1.

[0202] Similarly to the preparation examples above it is also possible to prepare the compounds listed in Tables 1 to 3. In the tables, the symbol

denotes the bond through which the radical in question is attached to the nitrogen atom of the skeleton.

[0203] Since in most cases the compounds are present as mixtures of the avermectin derivatives B1a and B1b, characterization by customary physical data such as melting point or refractive index makes little sense. For this reason, the compounds are characterized by the retention times which are determined in an analysis by HPLC (high performance liquid chromatography). Here, the term B1a refers to the main component in which R₁ is sec-butyl, with a content of usually more than 80%. B1b denotes the minor component in which R₁ is isopropyl. The compounds where two retention times are given both for the B1a and for the B1b derivative are mixtures of diastereomers which can be separated chromatographically. In the case of compounds where a retention time is given only in column B1a or only in column B1b, the pure B1a or B1b component, respectively, can be obtained during work-up. The correct structures of the B1a and B1b components are assigned by mass spectrometry.

[0204] The following method is used for HPLC analysis: HPLC radient conditions Solvent A: 0.01% of trifluoroacetic acid in H₂O Solvent B: 0.01% of trifluoroacetic acid in CH₃CN Flow rate Time [min] A [%] B [%] [μl/min]  0 80 20 500  0.1 50 50 500 10 5 95 500 15 0 100 500 17 0 100 500 17.1 80 20 500 22 80 20 500 Column: YMC-Pack ODS-AQ Column length: 125 mm Internal diameter of the column:  2 mm Temperature: 40° C.

[0205] The YMC-Pack ODS-AQ column used for the chromatography of the compounds is manufactured by YMC, Alte Raesfelderstrasse 6, 46514 Schermbeck, Germany. TABLE 1 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₂ is hydrogen. Retention time (min) No. R₃ B1a B1b 1.001

7.64 7.06 1.002

5.92 5.62 1.003 (3-nitrophenyl)methyl 5.80 5.59 1.004 (4-dimethylaminophenyl)methyl 6.12 5.87 1.005 (3-bromophenyl)methyl 6.32 6.00 1.006

5.84 5.48 1.007 2-phenyl-n-propyl 6.62/6.41 6.20/6.00 1.008 3-pyridylmethyl 5.96 5.61 1.009 (2,4-dimethylphenyl)methyl 6.59 6.22 1.010 (3-fluorophenyl)methyl 5.80 5.46 1.011

6.18 5.87 1.012

5.39 5.14 1.013

7.11 6.72 1.014 (3,4-methylenedioxy-6-nitrophenyl)methyl 6.01 5.66 1.015

8.37 7.75 1.016 (2-hydroxy-5-methoxyphenyl)methyl 5.64 5.26 1.017 (2-hydroxy-4-methoxyphenyl)methyl 5.81 5.55 1.018 (2,3-dihydroxyphenyl)methyl 5.45 5.10 1.019 (2-hydroxy-5-nitrophenyl)methyl 6.28 5.92 1.020

6.73 6.34 1.021 dec-4-en-1-yl 7.96 7.54 1.022 (3-[4-methoxyphenoxy]phenyl)methyl 7.00 6.62 1.023

6.63 6.25 1.024 3-phenyl-n-propyl 7.03 6.65 1.025 4-pyridylmethyl 5.40 5.07 1.026

4.57 4.32 1.027 ethyl 5.30 4.96 1.028 n-butyl 5.56 5.10 1.029

5.95 5.60 1.030 (2-bromophenyl)methyl 6.85 6.47 1.031

5.24 4.86 1.032

5.74 5.36 1.033 (4-n-propoxyphenyl)methyl 6.49 6.10 1.034

7.18 — 1.035 (2-chloro-4-hydroxyphenyl)methyl 6.30 5.87 1.036 cyclododecyl 9.2 8.80 1.037 1-methyl-n-butyl 6.76/6.98 6.33/6.50 1.038 4-hydroxy-1-methyi-n-butyl 6.25 5.70 1.039 1-methyl-n-propyl 7.50 6.81 1.040

6.50 6.10 1.041 (4-tert-butylphenyl)methyl 7.31 6.98 1.042 3-phenyl-n-butyl 7.22 6.90 1.043

6.84 6.56 1.044 —CH₂—C(═O)—CH₂-phenyl 7.15 6.76 1.045 —CH₂—C(═O)—O-methyl 5.75 5.39 1.046 —CH₂—C(═O)—O-ethyl 6.12 5.72 1.047

6.95 6.41 1.048

6.40 5.96 1.049

6.27 5.81 1.050

5.86 5.50 1.051

5.24 5.86 1.052

5.35 5.00 1.053

5.20 4.86 1.054 1,2-dimethyl-3-hydroxy-n-propyl 5.71 5.30 1.055 cyclobutyl 5.61 5.24 1.056

7.42 6.90 1.057

6.47 6.02 1.058 —CH₂C(═O)—O-i-propyl 5.93 5.72 1.059 —CH₂—C(═O)—O—CH₂—CH₂—O—CH₃ 5.44 5.21 1.060 —CH₂C(═O)—O-tert-butyl 6.15 5.97 1.061 —CH₂C(═O)NH₂ 4.83 4.58 1.062

6.13 5.67 1.063

3.46 3.26 1.064 propargyl 5.36 4.97 1.065 2-chloroallyl 5.93 5.51 1.066 3,3-dichloroallyl 6.12 5.72 1.067

5.97 5.59 1.068

5.57 5.24 1.069

1.070

1.071 1-cyclopropylethyl 1.072

1.073

1.074

1.075

1.076

1.077

1.078

1.079 3-methylcyclopentyl 1.080

1.081

1.082

1.083 (pentafluorophenyl)methyl 1.084 (2,3,5-trichlorophenyl)methyl 1.085 (2,3,6-trichlorophenyl)methyl 1.086 (2,3,4-trifluorophenyl)methyl 1.087 (2,6-dichlorophenyl)methyl 1.088 (2,3-dichlorophenyl)methyl 1.089 (2-hydroxy-3,5-dichlorophenyl)methyl 1.090 (2-chloro-6-fluorophenyl)methyl 1.091 (2-chloro-6-nitrophenyl)methyl 1.092 (3-chloro-4-nitrophenyl)methyl 1.093 (2-chloro-5-nitrophenyl)methyl 1.094 (2,6-difluorophenyl)methyl 1.095 (2,3-difluorophenyl)methyl 1.096 (2-hydroxy-5-bromophenyl)methyl 1.097 (2-hydroxy-5-chlorophenyl)methyl 1.098 (3-nitro-4-hydroxyphenyl)methyl 1.099 (3-hydroxy-4-nitrophenyl)methyl 1.100 (3-hydroxyphenyl)methyl 1.101 (2-hydroxyphenyl)methyl 1.102 (2,5-dihydroxyphenyl)methyl 1.103 3-trifluoromethylcyclohexyl 1.104

1.105

1.106

1.107 2-methoxycyclohexyl 1.108

1.109

1.110

1.111

1.112

1.113 (2-trifluoromethylphenyl)methyl 1.114 (3-trifluoromethoxyphenyl)methyl 1.115 (3-cyanophenyl)methyl 1.116 (2,3-methylenedioxyphenyl)methyl 1.117 (2-methoxy-5-bromophenyl)methyl 1.118 (3-bromo-4-hydroxy-5-methoxyphenyl)methyl 1.119 (2-nitro-3-methoxyphenyl)methyl 1.120 (4-methoxyphenyl)methyl 1.121 (3-hydroxy-4-methoxyphenyl)methyl 1.122

1.123 2-ethylhexyl 1.124

1.125

1.126 (3-pentafluoroethoxyphenyl)methyl 1.127

1.128

1.129 (3-bromo-4,6-dimethoxyphenyl)methyl 1.130 (2-bromo-4,5-dimethoxyphenyl)methyl 1.131

1.132 (2-nitro-4,5-dimethoxyphenyl)methyl 1.133 2-benzyloxyethyl 1.134 (3,5-dimethyl-4-hydroxyphenyl)methyl 1.135 (2-hydroxy-4,6-dimethoxyphenyl)methyl 1.136

1.137

1.138

1.139

1.140 (2,4,6-trimethylphenyl)methyl 1.141 3,7-dimethyloct-6-en-1-yl 1.142 naphth-1-yl 1.143 naphth-2-yl 1.144

1.145

1.146

1.147

1.148

1.149

1.150

1.151 n-dodecyl 1.152 (3-[3,4-dichlorophenoxy]phenyl)methyl 1.153 (3-[4-chlorophenoxy]phenyl)methyl 1.154

1.155

1.156

1.157

1.158

[0206] TABLE 2 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) or isopropyl (B1b) and R₂ is methyl: Retention time (min) No. R₃ B1a B1b 2.001 benzyl 6.20 5.75 2.002 allyl 5.53 5.25 2.003 —CH₂—C(═O)—O-ethyl 6.57 6.05 2.004 2-hydroxyethyl 4.27 3.97 2.005 —CH₂—C(═O)—O-methyl 6.09 5.66 2.006 but-2-en-1-yl 6.11 5.66 2.007

7.53 7.08 2.008 —CH₂—C(═O)—O-t-butyl 7.05 6.59 2.009 (4-fluoro-2-trifluoromethylphenyl)methyl 9.49 8.97 2.010 (4-fluoro-3-trifluoromethylphenyl)methyl 7.25 6.61 2.011 (3,4-difluorophenyl)methyl 6.55 6.11 2.012 isopropyl 4.48 4.13 2.013 (3-trifluoromethylphenyl)methyl 7.38 6.96 2.014

6.40 5.99 2.015 2-methylallyl 6.19 5.88 2.016 —CH₂—C(═O)—OH 6.42 5.91 2.017 —CH₂—C(═32O)—NH₂ 5.27 4.97 2.018

8.18 7.69 2.019 (2-methylphenyl)methyl 7.02 6.59 2.020

6.55 6.15 2.021

5.20 5.00 2.022 ethyl 5.11 4.67 2.023

7.08 6.62 2.024

6.95 6.55 2.025

4.98 4.55 2.026 (4-phenylphenyl)methyl 7.84 7.43 2.027

7.86 7.59 2.028

6.56 6.12 2.029 (4-t-butylphenyl)methyl 8.32 7.94 2.030 (4-fIuorophenyl)methyl 6.88 6.49 2.031 (4-bromophenyl)methyl 7.50 7.07 2.032 2-bromoallyl 2.033 —CH₂—C(═O)—O-i-propyl 2.034 —CH₂—C(═O)—O—CH₂—CH₂—O—CH₃ 2.035 (2,3,4-trifluorophenyl)methyl 2.036 (2,4,5-trifluorophenyl)methyl 2.037 (2,3,6-trifluorophenyl)methyl 2.038 (3,5-dibromophenyl)methyl 2.039 (3-fIuoro-6-bromophenyl)methyl 2.040 (2,3-dichlorophenyl)methyl 2.041 (2,6-dichlorophenyl)methyl 2.042 (2,5-dichlorophenyl)methyl 2.043 (3,4-dichlorophenyl)methyl 2.044 (2-fluoro-3-chlorophenyl)methyl 2.045 (2-chloro-4-fluorophenyl)methyl 2.046 (2,5-difluorophenyl)methyl 2.047 (2,6-difluorophenyl)methyl 2.048 (2,3-difluorophenyl)methyl 2.049 (3,5-difluorophenyl)methyl 2.050 (2-bromophenyl)methyi 2.051 (2-chlorophenyl)methyl 2.052 (2-fluorophenyl)methyl 2.053 (3-fluorophenyl)methyl 2.054 (4-iodophenyl)methyl 2.055 (2-iodophenyl)methyl 2.056 (4-nitrophenyl)methyl 2.057 (3-nitrophenyl)methyl 2.058

2.059

2.060 (3,5-dichlorophenyl)methyl 2.061 (2-trifluoromethylphenyl)methyl 2.062 (3-trifluoromethoxyphenyl)methyl 2.063 (4-cyanophenyl)methyl 2.064 (2-cyanophenyl)methyl 2.065 (3-cyanophenyl)methyl 2.066 (2,3-dichloro-4-methoxyphenyl)methyl 2.067

2.068 (4-difluoromethoxyphenyl)methyl 7.88 7.56 2.069 (2-fluoro-3-methylphenyl)methyl 2.070

2.071

2.072

2.073

2.074

2.075 (3,5-dimethylphenyl)methyl 2.076 (2-methoxy-4-methoxycarbonylphenyl)methyl 2.077

2.078

6.94 6.67 2.079 (2-phenylphenyl)methyl 2.080 (4-phenylphenyl)methyl 2.081

2.082 n-propyl 2.083 isopropyl 2.084 n-butyl 2.085 n-pentyl 2.086 n-hexyl 2.087 n-heptyl 2.088 n-octyl 2.089 isobutyl 2.090 sec-butyl 2.091 tert-butyl 2.092 isopentyl 2.093 neopentyl 2.094 isohexyl 2.095

5.61 5.18

[0207] TABLE 3 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) or isopropyl (B1b): Retention time (min) No. R₂ R₃ B1a B1b 3.001 3-phenylallyl 3-phenylallyl 8.54 8.08 3.002

5.69 5.28 3.003

5.50 5.13 3.004 3-phenyl-n-propyl 3-phenyl-n-propyl 8.46 7.99 3.005 3,7-dimethyloct-6-en-1-yl 3,7-dimethyloct-6-en-1-yl 10.74 10.57 3.006 ethyl

8.28 — 3.007 ethyl ethyl 5.73 5.31 3.008

9.11 8.64 3.009

8.34 7.85 3.010

5.39 5.12 3.011

5.53 5.15 3.012

10.75 10.36 3.013 ethyl benzyl 3.014 ethyl allyl 3.015 ethyl

3.016 3-methyl-n-butyl 3-methyl-n-butyl 3.017 3-phenyl-n-butyl 3-phenyl-n-butyl 3.018 ethyl n-propyl 3.019 ethyl isopropyl 3.020 ethyl n-butyl 3.021 ethyl pentyl 3.022 ethyl hexyl 3.023 ethyl heptyl 3.024 ethyl n-octyl 3.025 ethyl sec-butyl 3.026 ethyl tert-butyl 3.027 ethyl isopentyl 3.028 ethyl neopentyl 3.029 ethyl isohexyl

[0208] Formulation examples for use in crop protection (%=per cent by weight) Example F1: Emulsion concentrates a) b) c) Active compound 25% 40% 50% Calcium dodecylbenzenesulphonate  5%  8%  6% Castor oil polyethylene glycol ether (36 mol of EO)  5% — — Tributylphenol polyethylene glycol ether (30 mol — 12%  4% of EO) Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%

[0209] Mixing of finely ground active compound and additives gives an emulsion concentrate which, by dilution with water, affords emulsions of the desired concentration. Example F2: Solutions a) b) c) d) Active compound 80% 10%  5% 95% Ethylene glycol monomethyl ether 20% — — Polyethylene glycol (MW 400) — 70% — N-methylpyrrolid-2-one 20% — — — Epoxidized coconut oil — — —  1% Petroleum ether (boiling range: 160-190°) — — 94% —

[0210] Mixing of finely ground active compound and additives gives a solution suitable for use in the form of microdrops. Example F3: Granules a) b) c) d) Active compound  5% 10%  8% 21% Kaolin 94% — 79% 54% Finely divided silicic acid  1% — 13%  7% Attapulgite — 90% — 18%

[0211] The active compound is dissolved in dichloromethane, the solution is sprayed onto the mixture of carriers and the solvent is evaporated under reduced pressure. Example F4: Wettable powder a) b) c) Active compound 25% 50% 75% Sodium lignosulphonate  5%  5% — Sodium lauryl sulphate  3% —  5% Sodium diisobutylnaphthalene sulphonate —  6% 10% Octylphenol polyethylene glycol ether (7-8 mol of —  2% — EO) Finely divided silicic acid  5% 10% 10% Kaolin 62% 27% —

[0212] Active compound and additives are mixed and the mixture is ground in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of the desired concentration. Example F5: Emulsion concentrate Active compound 10% Octylphenol polyethylene glycol ether (4-5 mol of EO)  3% Calcium dodecylbenzenesulphonate  3% Castor oil polyethylene glycol ether (36 mol of EO)  4% Cyclohexanone 30% Xylene mixture 50%

[0213] Mixing of finely ground active compound and additives gives an emulsion concentrate which, by dilution with water, affords emulsions of the desired concentration. Example F6: Extruder granules Active compound 10% Sodium lignosulphonate  2% Carboxymethylcellulose  1% Kaolin 87%

[0214] Active compound and additives are mixed, the mixture is ground, moistened with water, extruded and granulated, and the granules are dried in a stream of air. Example F7: Coated granules Active compound  3% Polyethylene glycol (MW 200)  3% Kaolin 94%

[0215] In a mixer, the finely ground active compound is applied uniformly to the kaolin which has been moistened with polyethylene glycol. This gives dust-free coated granules. Example F8: Suspension concentrate Active compound 40% Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol of EO)  6% Sodium lignosulphonate 10% Carboxymethylcellulose  1% Aqueous formaldehyde solution (37%) 0.2%  Aqueous silicone oil emulsion (75%) 0.8%  Water 32%

[0216] Mixing of finely ground active compound and additives gives a suspension concentrate which, by dilution with water, affords suspensions of the desired concentration.

Biological Examples Example B1 Activity against Spodoptera littoralis

[0217] Young soya bean plants are sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm of active compound, and, after the spray coating has dried on, populated with 10 caterpillars of the first stage of Spodoptera littoralis and then introduced into a plastic container. 3 days later, the reduction in the population in per cent and the reduction in the feeding damage in per cent (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and the untreated plants.

[0218] In this test, the compounds of the tables show good activity. Thus, in particular the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.044, 1.045 1.046, 1.047, 1.048, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.059, 1.060, 1.061, 1.062, 1.063, 1.064, 1.065, 1.066, 1.067, 1.068, 1.069, 1.070, 1.071, 1.072, 1.073, 1.074, 1.075, 1.076, 1.077, 1.078, 1.079, 1.080, 1.081, 1.082, 1.083, 1.084, 1.085, 1.086, 1.087, 1.088, 1.089, 1.090, 1.091, 1.092, 1.093, 1.094, 1.095, 1.096, 1.097, 1.098, 1.099, 1.100, 1.101, 1.102, 1.103, 1.104, 1.106, 1.107, 1.109, 1.110, 1.111, 1.112, 1.113, 1.114, 1.115, 1.116, 1.117, 1.118, 1.119, 1.120, 1.121, 1.122, 1.123, 1.124, 1.125, 1.126, 1.127, 1.128, 1.129, 1.130, 1.131, 1.132, 1.133, 1.134, 1.135, 1.136, 1.137, 1.138, 1.139, 1.140, 1.141, 1.142, 1.143, 1.144, 1.145, 1.146, 1.147, 1.148, 1.149, 1.150, 1.151, 1.152, 1.153, 1.154, 1.155, 1.156, 1.157, 1.158, 2.001, 2.002, 2.003, 2.004, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, 2.011, 2.012, 2.013, 2.014, 2.015, 2.016, 2.017, 2.018, 2.019, 2.020, 2.021, 2.022, 2.023, 2.024, 2.025, 2.026, 2.027, 2.028, 2.029, 2.030, 2.031, 2.032, 2.033, 2.034, 2.035, 2.036, 2.037, 2.038, 2.039, 2.040, 2.041, 2.042, 2.043, 2.044, 2.045, 2.046, 2.047, 2.048, 2.049, 2.050, 2.051, 2.052, 2.053, 2.054, 2.055, 2.056, 2.057, 2.058, 2.059, 2.060, 2.061, 2.062, 2.063, 2.064, 2.065, 2.066, 2.067, 2.068, 2.069, 2.070, 2.071, 2.072, 2.073, 2.074, 2.075, 2.076, 2.077, 2.078, 2.079, 2.080, 2.081, 3.001, 3.002, 3.003, 3.004, 3.005, 3.006, 3.007, 3.008, 3.009, 3.010, 3.011 and 3.012 effect a reduction in the pest population by more than 80%.

Example B2 Activity against Spodoptera littoralis, Systemic

[0219] Maize seedlings are placed into the test solution. After 6 days, the leaves are cut off, placed onto moist filter paper in a Petri dish and infested with 12 to 15 Spodoptera littoralis larvae of the L₁ stage. 4 days later, the reduction of the population in per cent (% activity) is determined by comparing the number of dead caterpillars between the treated and the untreated plants.

[0220] In this test, the compounds of the tables show good activity. Thus, in particular the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.044, 1.045 1.046, 1.047, 1.048, 1.049, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.059, 1.060, 1.061, 1.062, 1.064, 1.065, 1.066, 1.067, 1.068, 1.069, 1.070, 1.071, 1.072, 1.073, 1.074, 1.075, 1.076, 1.077, 1.078, 1.079, 1.080, 1.081, 1.082, 1.083, 1.084, 1.085, 1.086, 1.087, 1.088, 1.089, 1.090, 1.091, 1.092, 1.093, 1.094, 1.095, 1.096, 1.097, 1.098, 1.099, 1.100, 1.101, 1.102, 1.103, 1.104, 1.105, 1.106, 1.107, 1.108, 1.109, 1.110, 1.111, 1.112, 1.113, 1.114, 1.115, 1.116, 1.117, 1.118, 1.119, 1.120, 1.121, 1.122, 1.123, 1.124, 1.125, 1.126, 1.127, 1.128, 1.129, 1.130, 1.131, 1.132, 1.133, 1.134, 1.135, 1.136, 1.137, 1.138, 1.139, 1.140, 1.141, 1.142, 1.143, 1.144, 1.145, 1.146, 1.147, 1.148, 1.149, 1.150, 1.151, 1.152, 1.153, 1.154, 1.155, 1.156, 1.157, 1.158, 2.001, 2.002, 2.003, 2.004, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, 2.011, 2.012, 2.013, 2.014, 2.015, 2.016, 2.017, 2.018, 2.019, 2.020, 2.021, 2.022, 2.023, 2.024, 2.025, 2.026, 2.027, 2.028, 2.029, 2.030, 2.031, 2.032, 2.033, 2.034, 2.035, 2.036, 2.037, 2.038, 2.039, 2.040, 2.041, 2.042, 2.043, 2.044, 2.045, 2.046, 2.047, 2.048, 2.049, 2.050, 2.051, 2.052, 2.053, 2.054, 2.055, 2.056, 2.057, 2.058, 2.059, 2.060, 2.061, 2.062, 2.063, 2.064, 2.065, 2.066, 2.067, 2.068, 2.069, 2.070, 2.071, 2.072, 2.073, 2.074, 2.075, 2.076, 2.077, 2.078, 2.079, 2.080, 2.081, 3.001, 3.002, 3.003, 3.004, 3.005, 3.006, 3.007, 3.008, 3.009, 3.010, 3.011 and 3.012 effect a reduction in the pest population by more than 80%.

Example B3 Activity against Heliothis virescens

[0221] 30-35 0- to 24-hour-old eggs of Heliothis virescens are placed onto filter paper in a Petri dish on a layer of synthetic feed. 0.8 ml of the test solution is then pipetted onto the filter papers. Evaluation is carried out after 6 days. The reduction in the population in per cent (% activity) is determined by comparing the number of dead eggs and larvae on the treated and the untreated plants [sic].

[0222] In this test, the compounds of the tables show good activity. Thus, in particular the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.044, 1.045, 1.047, 1.048, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.069, 1.070, 1.071, 1.072, 1.073, 1.074, 1.075, 1.076, 1.078, 1.079, 1.080, 1.081, 1.082, 1.083, 1.084, 1.085, 1.086, 1.087, 1.088, 1.089, 1.090, 1.091, 1.092, 1.093, 1.094, 1.095, 1.096, 1.097, 1.098, 1.099, 1.100, 1.101, 1.102, 1.103, 1.104, 1.107, 1.109, 1.110, 1.111, 1.112, 1.113, 1.114, 1.115, 1.116, 1.117, 1.118, 1.119, 1.120, 1.121, 1.122, 1.123, 1.124, 1.125, 1.126, 1.127, 1.128, 1.129, 1.130, 1.131, 1.132, 1.133, 1.134, 1.135, 1.136, 1.137, 1.138, 1.139, 1.140, 1.141, 1.142, 1.143, 1.144, 1.145, 1.147, 1.148, 1.149, 1.150, 1.151, 1.152, 1.153, 1.154, 1.155, 1.156, 1.157, 1.158, 2.001, 2.002, 2.003, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, 2.011, 2.012, 2.013, 2.014, 2.015, 2.016, 2.017, 2.018, 2.019, 2.020, 2.021, 2.026, 2.027, 2.028, 2.029, 2.030, 2.031, 2.032, 2.033, 2.034, 2.035, 2.036, 2.037, 2.038, 2.039, 2.040, 2.042, 2.043, 2.044, 2.045, 2.046, 2.047, 2.048, 2.049, 2.050, 2.051, 2.052, 2.053, 2.054, 2.055, 2.056, 2.057, 2.058, 2.059, 2.062, 2.063, 2.064, 2.066, 2.067, 2.068, 2.069, 2.070, 2.071, 2.073, 2.074, 2.075, 2.076, 2.077, 2.078, 2.079, 2.080, 2.081, 3.001, 3.002, 3.003, 3.004, 3.005, 3.006, 3.007, 3.008, 3.009 and 3.010 effect a reduction in the pest population by more than 80%.

Example B4 Activity against Plutella xylostella Caterpillars

[0223] Young cabbage plants are sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm ppm [sic] of the active compound. After the spray coating has dried on, the cabbage plants are populated with 10 caterpillars of the first stage of Plutella xylostella and introduced into a plastic container. Evaluation is carried out after 3 days. The reduction in the population in per cent and the reduction in the feeding damage in per cent (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated and the untreated plants.

[0224] In this test, the compounds of Table 1 [sic] show good activity against Plutella xylostella. Thus, in particular the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.046, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.060, 1.061, 1.070, 1.075, 1.082, 1.083, 1.084, 1.085, 1.086, 1.087, 1.088, 1.089, 1.090, 1.091, 1.092, 1.093, 1.094, 1.095, 1.096, 1.097, 1.098, 1.099, 1.100, 1.101, 1.102, 1.104, 1.113, 1.114, 1.115, 1.116, 1.117, 1.118, 1.119, 1.120, 1.121, 1.122, 1.123, 1.125, 1.126, 1.127, 1.128, 1.129, 1.130, 1.131, 1.132, 1.133, 1.134, 1.135, 1.138, 1.140, 1.141, 1.142, 1.143, 1.144, 1.145, 1.147, 1.149, 1.151, 1.152, 1.153, 1.154, 1.155, 1.156, 1.157, 1.158, 2.001, 2.002, 2.003, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, 2.011, 2.012, 2.013, 2.014, 2.015, 2.017, 2.018, 2.019, 2.020, 2.021, 2.022, 2.026, 2.027, 2.028, 2.029, 2.030, 2.031, 2.032, 2.033, 2.034, 2.035, 2.042, 2.046, 2.057, 2.068, 2.070, 2.073, 2.077, 2.078, 3.001, 3.002, 3.003, 3.004, 3.005, 3.006, 3.007, 3.008 and 3.009 effect a reduction in the pest population by more than 80%.

Example B5 Activity against Frankliniella occidentalis

[0225] In Petri dishes, discs of the leaves of beans are placed onto agar and sprayed with test solution in a spraying chamber. The leaves are then infested with a mixed population of Frankliniella occidentalis. Evaluation is carried out after 10 days. The reduction in per cent (% activity) is determined by comparing the population on the treated leaves with that of the untreated leaves.

[0226] In particular the compounds 1.027, 1.037, 1.038, 1.039, 1.040, 1.050, 1.061, 1.065, 1.068, 1.082, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, 2.011, 2.012, 2.013, 2.014, 2.015, 2.016, 2.017, 2.018, 2.020, 2.021, 2.026, 2.027, 2.028, 2.029, 2.030, 2.032, 2.033, 2.034, 2.036, 2.038, 2.040, 2.042, 2.046, 2.047, 2.049, 2.050, 2.051, 2.055, 2.057, 2.062, 2.070, 2.071, 2.072, 3.003, 3.006 and 3.012 effect a reduction in the pest population by more than 80%.

Example B6 Activity against Diabrotica balteata

[0227] Maize seedlings are sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm of active compound and, after the spray coating has dried on, populated with 10 larvae of the second stage of Diabrotica balteata and then introduced into a plastic container. After 6 days, the reduction in the population in per cent (% activity) is determined by comparing the number of dead larvae between the treated and the untreated plants.

[0228] In this test, the compounds of the tables show good activity. Thus, in particular the compounds 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.045, 1.046, 1.047, 1.048, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.059, 1.063, 1.064, 1.065, 1.066, 1.067, 1.068, 1.069, 1.070, 1.071, 1.072, 1.074, 1.075, 1.076, 1.077, 1.078, 1.079, 1.080, 1.081, 1.082, 1.083, 1.084, 1.085, 1.086, 1.087, 1.088, 1.090, 1.091, 1.092, 1.093, 1.094, 1.095, 1.096, 1.097, 1.098, 1.099, 1.100, 1.101, 1.102, 1.104, 1.105, 1.107, 1.108, 1.109, 1.111, 1.113, 1.114, 1.115, 1.116, 1.117, 1.118, 1.119, 1.120, 1.121, 1.122, 1.123, 1.125, 1.126, 1.127, 1.128, 1.129, 1.130, 1.131, 1.132, 1.133, 1.134, 1.135, 1.136, 1.137, 1.138, 1.139, 1.140, 1.141, 1.142, 1.143, 1.144, 1.145, 1.147, 1.148, 1.149, 1.150, 1.151, 1.152, 1.153, 1.154, 1.155, 1.156, 1.157, 1.158, 2.001, 2.002, 2.003, 2.004, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, 2.011, 2.012, 2.013, 2.014, 2.015, 2.016, 2.017, 2.018, 2.019, 2.020, 2.021, 2.022, 2.025, 2.026, 2.027, 2.028, 2.030, 2.031, 2.032, 2.033, 2.034, 2.046, 2.050, 2.051, 2.052, 2.056, 2.073, 2.074, 2.076, 2.077, 3.001, 3.002, 3.004, 3.006, 3.007, 3.008 and 3.009 effect a reduction in the pest population by more than 80%.

Example B7 Activity against Tetranychus urticae

[0229] Young bean plants are populated with a mixed population of Tetranychus urticae and, after 1 day, sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm of active compound, incubated at 25° C. for 6 days and then evaluated. The reduction in the population in per cent (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated and on the untreated plants.

[0230] In this test, the compounds of the tables show good activity. Thus, in particular the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.044, 1.045 1.046, 1.047, 1.048, 1.049, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.059, 1.060, 1.061, 1.062, 1.063, 1.064, 1.065, 1.066, 1.067, 1.068, 1.069, 1.070, 1.071, 1.072, 1.073, 1.074, 1.075, 1.076, 1.077, 1.078, 1.079, 1.080, 1.081, 1.082, 1.083, 1.084, 1.085, 1.086, 1.087, 1.088, 1.089, 1.090, 1.091, 1.092, 1.093, 1.094, 1.095, 1.096, 1.097, 1.098, 1.099, 1.100, 1.101, 1.102, 1.103, 1.104, 1.105, 1.106, 1.107, 1.108, 1.109, 1.110, 1.111, 1.112, 1.113, 1.114, 1.115, 1.116, 1.117, 1.118, 1.119, 1.120, 1.121, 1.122, 1.123, 1.124, 1.126, 1.127, 1.128, 1.129, 1.130, 1.131, 1.132, 1.133, 1.134, 1.135, 1.136, 1.137, 1.138,.1.139, 1.140, 1.141, 1.142, 1.143, 1.144, 1.145, 1.146, 1.147, 1.148, 1.149, 1.150, 1.151, 1.152, 1.153, 1.154, 1.155, 1.156, 1.157, 1.158, 2.001, 2.002, 2.003, 2.004, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, 2.011, 2.012, 2.013, 2.014, 2.015, 2.016, 2.017, 2.018, 2.019, 2.020, 2.021, 2.022, 2.023, 2.024, 2.025, 2.026, 2.027, 2.028, 2.029, 2.030, 2.031, 2.032, 2.033, 2.034, 2.035, 2.036, 2.037, 2.038, 2.039, 2.040, 2.041, 2.042, 2.043, 2.044, 2.045, 2.046, 2.047, 2.048, 2.049, 2.051, 2.052, 2.053, 2.054, 2.055, 2.056, 2.057, 2.058, 2.059, 2.060, 2.061, 2.062, 2.063, 2.064, 2.065, 2.066, 2.067, 2.068, 2.069, 2.070, 2.071, 2.072, 2.073, 2.074, 2.075, 2.076, 2.077, 2.078, 2.079, 2.081, 3.001, 3.002, 3.003, 3.004, 3.005, 3.006, 3.007, 3.008, 3.009, 3.010, 3.011 and 3.012 effect a reduction in the pest population by more than 80%. 

What is claimed is:
 1. A compound of the formula

in which R₁ is C₁-C₁₂alkyl, C₃-C₈cycloalkyl or C₂-C₁₂alkenyl; R₂ is H, unsubstituted or mono- to pentasubstituted C₁-C₁₂alkyl or unsubstituted or mono- to pentasubstituted C₂-C₁₂alkenyl; R₃ is C₂-C₁₂alkyl, mono- to pentasubstituted C₁-C₁₂alkyl, unsubstituted or mono- to pentasubstituted C₃-C₁₂cycloalkyl, unsubstituted or mono- to pentasubstituted C₂-C₁₂alkenyl, unsubstituted or mono- to pentasubstituted C₂-C₁₂alkynyl; or R₂ and R₃ together are a three- to seven-membered alkylene or a four- to seven-membered alkenylene bridge, in which a CH₂ group may be substituted by O, S or NR₄; in which the substituents of the alkyl, alkenyl, alkynyl, alkylene, alkenylene and cycloalkyl radicals mentioned are selected from the group consisting of OH, halogen, halo-C₁-C₂alkyl, CN, NO₂, C₂-C₆alkynyl, C₃-C₈-cycloalkyl which is unsubstituted or substituted by one to three methyl groups, norbornylenyl, C₃-C₈-cycloalkenyl which is unsubstituted or substituted by one to three methyl groups, C₃-C₈halocycloalkyl, C₁-C₁₂alkoxy, C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₈cycloalkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₃-C₈cycloalkylthio, C₁-C₁₂-haloalkylthio, C₁-C₁₂alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₁₂haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl, C₁-C₁₂alkylsulfonyl, C₃-C₈cycloalkylsulfonyl, C₁-C₁₂haloalkylsulfonyl, C₃-C₈halocycloalkylsulfonyl, C₂-C₈alkenyl, C₂-C₈alkynyl, NH(C₁-C₆alkyl), N(C₁-C₆alkyl)₂, —C(═O)R₅, —NHC(═O)R₆, —P(═O)(OC₁-C₆alkyl)₂; aryl, heterocyclyl, aryloxy, heterocyclyloxy; and also aryl, heterocyclyl, aryloxy and heterocyclyloxy which, depending on the possibilities of substitution on the ring, are mono- to pentasubstituted by substituents selected from the group consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl, dimethylamino-C₁-C₆alkoxy, C₂-C₈alkenyl, C₂-C₈alkynyl, phenoxy, phenyl-C₁-C₆alkyl; phenoxy which is unsubstituted or mono- to trisubstituted independently of one another by halogen, methoxy, trifluoromethyl or trifluoromethoxy; phenyl-C₁-C₆alkoxy which is unsubstituted or mono- to trisubstituted in the aromatic ring independently of one another by halogen, methoxy, trifluoromethyl or trifluoromethoxy; phenyl-C₂-C₆alkenyl, phenyl-C₂-C₆alkynyl, methylenedioxy, —C(═O)R₅, —O—C(═O)R₆, —NH—C(═O)R₆, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl and C₃-C₈halocycloalkylsulfonyl; R₄ is C₁-C₈alkyl, C₃-C₈cycloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, benzyl or —C(═O)—R₅; R₅ is H, OH, SH, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₁₂alkylthio, C₂-C₈alkenyloxy, C₂-C₈alkynyloxy; phenyl, phenoxy, benzyloxy, NH-phenyl, —N(C₁-C₆alkyl)-phenyl, NH—C₁-C₆alkyl-C(═O)—R₇, —N(C₁-C₆alkyl)-C₁-C₆alkyl-C(═O)—R₇; or phenyl, phenoxy, benzyloxy, NH-phenyl or —N(C₁-C₆alkyl)-phenyl which are mono to trisubstituted in the aromatic ring independently of one another by halogen, C₁-C₆alkoxy, C₁-C₆haloalkyl or C₁-C₆haloalkoxy; R₆ is H, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, phenyl, benzyl, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, —NH-phenyl or —N(C₁-C₁₂alkyl)-phenyl; and R₇ is H, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₂-C₈alkenyloxy, phenyl, phenoxy, benzyloxy, NH₂, NH(C₁-C₁₂alkyl), N(C₁-C₁₂alkyl)₂, —NH-phenyl or —N(C₁-C₁₂alkyl)-phenyl; with the proviso that R₁ is not sec-butyl or isopropyl if R₂ is H and R₃ is 2-hydroxyethyl, isopropyl, n-octyl or benzyl; or, if appropriate, an E/Z isomer, E/Z isomer mixture and/or tautomer.
 2. A pesticide which contains at least one compound of the formula (I) as described in claim 1 as active compound and at least one auxiliary.
 3. A method for controlling pests wherein a composition as described in claim 2 is applied to the pests or their habitat.
 4. A process for preparing a composition as described in claim 2 which contains at least one auxiliary, wherein the active compound is mixed intimately and/or ground with the auxiliary (or auxiliaries).
 5. The use of a compound of the formula (I) as described in claim 1 for preparing a composition as described in claim
 2. 6. The use of a composition as described in claim 2 for controlling pests.
 7. A method according to claim 3 for protecting plant propagation material, wherein the propagation material or the location where the propagation material is planted is treated.
 8. Plant propagation material treated in accordance with the method described in claim
 7. 